WO2016128133A1 - Dispositifs électroniques comportant des couches tampons d'oxyde métallique pouvant être traitées par solutions - Google Patents

Dispositifs électroniques comportant des couches tampons d'oxyde métallique pouvant être traitées par solutions Download PDF

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Publication number
WO2016128133A1
WO2016128133A1 PCT/EP2016/000220 EP2016000220W WO2016128133A1 WO 2016128133 A1 WO2016128133 A1 WO 2016128133A1 EP 2016000220 W EP2016000220 W EP 2016000220W WO 2016128133 A1 WO2016128133 A1 WO 2016128133A1
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Prior art keywords
layers
metal oxide
electrode
buffer layer
metal
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PCT/EP2016/000220
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English (en)
Inventor
Norman Albert LÜCHINGER
Benjamin HARTMEIER
Yi HOU
Tobias STUBHAN
Christoph Brabec
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Nanograde Ag
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Priority to BR112017016097-8A priority Critical patent/BR112017016097B1/pt
Priority to KR1020177025149A priority patent/KR102120534B1/ko
Priority to CA2974044A priority patent/CA2974044A1/fr
Priority to SG11201706566XA priority patent/SG11201706566XA/en
Priority to CN201680010254.9A priority patent/CN107251256B/zh
Priority to JP2017542065A priority patent/JP6503080B2/ja
Application filed by Nanograde Ag filed Critical Nanograde Ag
Priority to AU2016218562A priority patent/AU2016218562A1/en
Priority to US15/550,439 priority patent/US10003037B2/en
Priority to RU2017131626A priority patent/RU2017131626A/ru
Priority to EP16704541.8A priority patent/EP3257091B1/fr
Publication of WO2016128133A1 publication Critical patent/WO2016128133A1/fr
Priority to ZA2017/05904A priority patent/ZA201705904B/en

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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/30—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains
    • H10K30/353—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains comprising blocking layers, e.g. exciton blocking layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/20—Carbon compounds, e.g. carbon nanotubes or fullerenes
    • H10K85/211—Fullerenes, e.g. C60
    • H10K85/215—Fullerenes, e.g. C60 comprising substituents, e.g. PCBM
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/02—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
    • H01L33/12—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies with a stress relaxation structure, e.g. buffer layer
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/20—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising organic-organic junctions, e.g. donor-acceptor junctions
    • H10K30/211—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising organic-organic junctions, e.g. donor-acceptor junctions comprising multiple junctions, e.g. double heterojunctions
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • H10K71/13—Deposition of organic active material using liquid deposition, e.g. spin coating using printing techniques, e.g. ink-jet printing or screen printing
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • H10K71/15—Deposition of organic active material using liquid deposition, e.g. spin coating characterised by the solvent used
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/50—Organic perovskites; Hybrid organic-inorganic perovskites [HOIP], e.g. CH3NH3PbI3
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
    • H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
    • H01L2031/0344—Organic materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/50—Photovoltaic [PV] devices
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to the field of electronic devices, particularly optoelectronic devices.
  • the invention further provides intermediate goods and materials suitable for manufacturing such devices, the invention also provides for specific manufacturing methods and for specific uses.
  • buffer layers in organic electronics, such as organic light emitting diodes (OLED) , organic photovoltaic cells (OPV cells) or perovskite type solar cells, in order to increase device efficiency and life- time.
  • Such buffer layers comprise metal oxides, such as zinc-, titanium-, tungsten-, nickel-, niobium- oxides, or doped metal oxides, such as Al-doped ZnO (“AZO") or Cu- doped NiO.
  • AZO Al-doped ZnO
  • Cu- doped NiO such as Al-doped ZnO
  • oxidic buffer layers are manufactured by thermal evaporation under high vacuum or by wet-chemical (precursor based) methods, requiring a high temperature annealing step; which is disadvantageous in terms of low-cost, large-area manufacturing processing.
  • O solar cells OLED
  • OLED organic solar cells
  • Such metal oxides in particulate form are known.
  • such oxidic layers are manufactured by thermal evaporation under high vacuum; which is disadvantageous in terms of low-cost, large-area manufacturing processing.
  • Such processes using comparatively high temperatures, e.g. by including an annealing step, are also disadvantageous in case the layer preceding the buffer layer is temperature sensitive.
  • the present inventors thus identified a need to provide manufacturing processes for buffer layers, particularly metal oxide buffer layers, that are compatible with temperature sensitive layers / materials.
  • Cs2C03 significantly influences work function of metal oxides in buffer layers. In certain applications, this is considered disadvantageous, as the desired properties of metal oxides interfere with the properties of Cs2C03.
  • the present inventors thus identified a need to provide metal oxide buffer layers with low or even zero amounts of Cs2C03.
  • Luechinger et al. (WO2014 /161100 ) describe organic electronic devices, such as OLEDs and organic solar cells, comprising buffer layers with surface modified metal oxide nanoparticles . Further, the advantages of solution processable buffer layers are outlined. Although simple in manufacturing, through its all-solution-process, the devices disclosed therein show comparatively low performance .
  • Kim et al. (Adv. Mater., 2014, DOI : 10.1002 /adma .201404189 ) describe perovskite-type organic solar cells comprising NiO and Cu-doped NiO buffer layers. Due to its manufacturing, the buffer layers are dense, i.e. not particulate. The devices show performances exceeding 15% PCE. Nevertheless it is considered disadvantageous that the metal oxide layers are applied by a wet chemical (precursor based) method and thus need to be thermally cured at very high temperatures. Accordingly, these devices are more difficult in manufacturing, as the remaining layers of the solar cells cannot withstand such high temperatures and thus need to be coated after the deposition of the buffer layer. Liu et al. (Chem.
  • the electro-optic device comprises an interfacial layer which is a blend of a metal oxide and at least one other material that provides at least one of a decrease in the work function or an increase of electrical conductivity compared to the metal oxide alone. Such other material being present in amounts of at least 10% and up to 120% and thus significantly influence the properties of the metal oxide.
  • Dong et al discloses the use of Cs2C03 as surface modification material for hybrid perovskite solar cells.
  • any device comprising functional thin films is encompassed, including inorganic LEDs or inorganic solar cells; but specifically organic electronics as defined below.
  • optical device is known in the field and denotes electronic devices that source, detect or control light. Accordingly, such devices either convert an electrical signal into an optical signal or vice versa.
  • organic electronics are known in the field and relate to electronic devices comprising a "substrate” and a multitude of layers, wherein at least one layer is a "buffer layer” as defined below. In organic electronics at least one layer comprises organic substances, essential to the correct functioning of said devices.
  • LED comprises both, organic LEDs (OLEDs) where the active layer comprises organic electrolumineszent materials (polymers or small molecule) , and Quantum dot LEDs (QLEDs) , where the active layer comprises electrolumineszent quantum dots.
  • OLEDs organic LEDs
  • QLEDs Quantum dot LEDs
  • Buffer layer denotes an interface layer in electronic devices, typically in devices as discussed herein.
  • Buffer layer is the general term for layers with a charge selective function such as hole transport (HTL) , hole injection (HIL) , hole extraction (HEL) , electron transport (ETL) , electron injection (EIL) or electron extraction (EEL) .
  • HTL hole transport
  • HIL hole injection
  • HEL hole extraction
  • ETL electron transport
  • EIL electron injection
  • EEL electron extraction
  • buffer layer is generally representing the different specific functions.
  • a buffer layer is often also referred as charge selective layer or charge transport layer (CTL) . Accordingly, the term buffer layer includes both, electron selective layers and hole selective layers.
  • Substrate denotes the layer on which the functional layers are applied on.
  • the substrate may be transparent or non-transparent. Suitable materials include organic materials, such as polymers and inorganic materials, such as glass.
  • physisorption is known in the field and is defined as adsorption in which the forces involved are intermolecular forces (van der Waals or electrostatic forces) and which do not involve a significant change in the electronic orbital patterns of the species involved, (see: "International Union of pure and Applied Chemistry” (http://goldbook.iupac.org/P04667.html) In the context of the present invention it denotes the adsorption of a molecule or ion on a surface by either electrostatic or van der Waals attraction. In contrast to chemisorption, a physisorbed molecule does not alter its chemical properties upon adsorption. Accordingly, by physisorption neither are covalent bonds formed or broken nor are atoms ionized or deionized.
  • scattering particles is known and describes materials that efficiently scatter light. Typically, scattering particles exhibit a high refractive index (such as > 2.0, preferably > 2.3) and a particle size in the range of the wavelength of visible light (such as 100 - 1000 nm, preferably 200 - 500 nm) .
  • Haze is known; the haze of a thin film is physically defined as the intensity of the diffuse transmission divided by the total transmission through the thin film. Haze can be measured with an integrated sphere.
  • active layer denotes a layer which is photoactive and either converts light into electrical energy (light absorbing; e.g. solar cells) or converts electrical energy into light (light emitting; e.g. LED's).
  • active layers contain one or more active materials.
  • the active layer of a solar cell comprises a fullerene-based compound such as PCBM (acceptor) and a second active material (donor) .
  • the active layer of a LED comprises organic materials, such as polymers or small molecules, such as discussed in Geffroy et al (Polym Int. 55:572 - 582 (2006) ) .
  • the active layer of a LED comprises electroluminescent quantum dots, such as Perovskite type crystals as disclosed e.g. in Kovalenko et al (Nanoletters 2014, DOI : 10.1021/nl5048779) .
  • active material denotes materials which are photoactive and either have electron acceptor or electron donor properties. This includes photoactive polymers, photoactive small molecules, photoactive quantum dots , photoactive metal-organic perovskites as used herein.
  • Perovskite and “Perovskite-type materials” are known in the field and are materials that exhibit the same crystalline structure as CaTi0 3 . They generally relate to crystalline materials complying with structure ABX3, whereby A and B are two cations of very different sizes; typically, A has a coordination number of 12 in respect to X, while B has a coordination number of 6 in respect to X.
  • Perovskite-type materials for example include metal organic halide materials such as methyl-ammonium-lead-iodide (CH 3 H3Pbl3) or methyl-ammonium-tin-iodide (CH3NH 3 Snl3) .
  • nanoparticle is known and particularly relates to solid amorphous or crystalline particles having at least one dimension in the size range of 1 - 100 nm.
  • nanoparticles are approximately isometric (such as spherical or cubic nanoparticles) .
  • Particles are considered approximately isometric, in case the aspect ratio (longest : shortest direction) of all 3 orthogonal dimensions is 1 - 2.
  • BET N 2 adsorption method
  • nanoparticle layer denotes a film composed of nanoparticles.
  • the thickness of the nanoparticle layer may vary over a broad range, but typically is 3 - 1000 nm, preferably 10 - 300 nm. If no scattering particles are present, the range is typically 3 - 1 000 nm, such as 3-30 nm for self-assembling monolayers. If scattering particles are present, the range is typically 100 - 20 000 nm preferably 1 000 - 10 000 nm.
  • a nanoparticle layer can be composed of a monolayer of nanoparticles, thus having a thickness equal to the size of the used nanoparticles and thus defining a lower limit of the thickness.
  • a nanoparticle layer can be composed of nanoparticles with a single size or with a bimodal or multimodal size distribution. Bimodal or multimodal size distributions are believed to result in a higher packing density of the nanoparticle layer. Further, the volume porosity of a nanoparticle layer typically is less than 95%, preferably less than 70%.
  • Metal oxide nanoparticles includes (i) nanoparticles of pure oxides, (ii) nanoparticles of doped oxides, (iii) mixed metal oxides and (iv) core shell nanoparticles, whereby the core and shell are composed of different oxides.
  • AZO is known in the field and includes Aluminum doped Zinc oxides meaning that the Aluminum is atomically dispersed in the Zinc oxide lattice (solid solution) .
  • solvent is known in the field and in the context of the present invention particularly includes water and polar organic solvents such as alcohols, glycol ethers, nitriles, ketones, esters, ethers, aldehydes, sulfoxides (such as dimethylsulfoxide (dmso)), formamides (such as diemthylformamide (dmf ) ) and acetamides (such as dimethylacetamide (dma) ) .
  • the above organic solvents can be substituted or unsubstituted and include linear, branched and cyclic derivatives. There can also be unsaturated bonds in the molecule.
  • the above organic solvents typically have 1 - 12 carbon atoms, preferably 1 - 7 carbon atoms.
  • dispenser and “dispersing agent” are known in the field and have essentially the same meaning. In the context of the present invention, these terms denote a substance, other than a solvent, which is used in suspensions of colloids to improve the separation of particles and to prevent agglomeration or settling. In the context of the present invention the terms “dispersant” and “dispersing agent” are used for the metal salts, stabilizing the nanoparticle suspensions disclosed herein
  • suspension is known and relates to a heterogeneous fluid of an internal phase (i.p.) that is a solid and an external phase (e.p.) that is a liquid.
  • a suspension typically has a kinetic stability of at least 1 day (measured according to complete particle sedimentation) .
  • the invention provides for a composition with (hydrodynamic size D90 of less than 100 nm) a shelf-life of more than 7 days, particularly more than 2 months.
  • the external phase typically comprises one or more solvents, such as water, alcohols and ketones and the like.
  • solution processing relates to the fabrication of organic electronics and intermediate goods comprising thin nanoparticle films by the use of one or more liquid suspensions; typically the application of the suspension (s) is/are conducted at ambient pressure.
  • Fig. 1 outlines the various aspects of the present invention.
  • the invention describes electronic devices from the group of organic electronics (DEV; IV. I - IV. Ill; 1 st aspect of the invention) having specific buffer layer(s); intermediate goods (INT; III, 2 nd aspect) suitable for manufacturing the above organic electronics; compositions in the form of a suspension (SUSP; II, 3 rd aspect) suitable for manufacturing the above intermediate goods by wet phase processing.
  • These compositions may be obtained by combining known starting materials, such as MOx nanoparticles (N.P.; I.I), metal salts (anion I. II and cation I. Ill) and solvents (SOLV; I. IV).
  • Fig. 2 shows a schematic setup of different types of intermediate goods (INT; III), useful for the manufacturing of organic electronics. According to figures III. A -III.D different sequences are shown where
  • (10) denotes a substrate [which can be transparent or non- transparent as well as organic (e.g. polymer) or inorganic (e.g. glass) ] ,
  • (20) denotes an electrode [which can be transparent or non- transparent] ,
  • (40) denotes an active layer [including e.g. a polymer, a small -molecule or a perovskite active material] ,
  • the second buffer layer (50) denotes a second buffer layer [with opposite polarization compared to the first buffer layer]
  • (60) denotes a second electrode [which can independently of the first electrode be transparent or non-transparent] .
  • the second buffer layer (50) may either have a composition according to the present invention, or may have a different composition, such as state-of-the art materials.
  • the inventive intermediates may comprise further layers or consist of the layers as shown in this figure.
  • Figure 3 schematically compares the internal structure of a buffer layer (30 or 50) on an electrode (20) depending on its manufacturing.
  • Figure 3A shows the structure as obtained by a nanoparticle deposition process, thus showing particulate metal oxide phases (2) and air in the form of pores (3) according to this invention.
  • Figure 3B shows the structure as obtained by either precursor based or vacuum deposition processes, thus showing a continuous / dense metal oxide phase (2) and air in the form of a varying amount of defects such as cracks or holes (3) .
  • the amount of defects in 3B may vary significantly.
  • Figure 4 shows a schematic illustration of a single metal oxide particle (I.I) as shown in figure 3, with the metal salt (cation I. Ill and anion I. II) adsorbed on its surface.
  • the metal salt cation I. Ill and anion I. II
  • the positively charged metal cation I. Ill
  • the negatively charged anion I. II
  • the anion may also be spatially separated (not shown) .
  • Figure 5 shows atomic force micrographs (10 x 10 micrometers) of films obtained according to example 5, left: this invention, right according to the prior art.
  • the invention relates to an electronic device, particularly selected from the group of optoelectronic devices, wherein said device comprises a substrate and a multitude of layers, wherein at least one of said layers is a buffer layer, wherein said buffer layer comprises metal oxide nanoparticles , wherein on the surface of said nanoparticles metal salts as described herein are physisorbed .
  • the invention relates to buffer layers in an electronic device, said buffer layers having a specific and beneficial composition containing metal oxide nanoparticles as described.
  • the present inventive buffer layers provide beneficial properties to the electronic devices because: (i) no post- treatment (e.g. plasma cleaning or annealing temperatures > 150°C) is required allowing an all-solution manufacturing process; (ii) only a very small amount of dispersing agent is needed thus leading to a high performance of the electronic devices.
  • no post- treatment e.g. plasma cleaning or annealing temperatures > 150°C
  • the device is selected from the group of organic solar cells (OPV, including perovskite type solar cells), organic light emitting diodes (OLED), organic photodetectors and quantum dot LED (QLED) ; particularly OPV and OLED, very particularly OPV.
  • OLED organic solar cells
  • QLED quantum dot LED
  • the invention relates to an OPV device with tandem architecture.
  • the invention relates to an OPV device with tandem architecture whereby an inventive layer of the present invention is part of the recombination layer .
  • the buffer layer is selected from the group consisting of hole transport (HTL) , hole injection (HIL) , hole extraction (HEL) , electron transport (ETL) , electron injection (EIL) and electron extraction (EEL) layers, preferably HTL, HIL, HEL.
  • the buffer layer is located on top of hydrophobic or hydrophilic organic materials, preferably PEDOT:PSS, photoactive polymers (absorbers or emitters) or photoactive small molecules (absorbers or emitters) .
  • the buffer layer is located on top of a hydrophilic inorganic material, preferably ITO or silver (including a vacuum deposited dense Ag layer or a solution processed porous Ag nanowire layer) .
  • the top and/or bottom electrode of the device is a silver, a copper or a nickel electrode, particularly a Ag-, Cu- or Ni- nano wire electrode.
  • the nano wires of such electrodes can be embedded in the hydrophilic or hydrophobic organic materials as defined above, particularly in PEDOT:PSS.
  • the top and bottom electrodes are both made from metal nanowires.
  • This embodiment provides transparent or semitransparent electronic devices.
  • the nano wires of such electrodes can be embedded in the hydrophilic or hydrophobic organic materials as defined above, particularly in PEDOTrPSS.
  • the top and/or bottom electrode is pure PED0T:PSS.
  • the top and/or bottom electrode is a combination of PEDOT:PSS with a regular metal collector grid (such as an Ag-, Cu- or Ni- collector grid) .
  • Metal oxide nanoparticles The term metal oxide nanoparticles is defined above. In one embodiment, the nanoparticles are selected from the group consisting of pure metal oxides, preferably Ni z O y (including NiO) , Zn 2 0 y (including ZnO) , Ti z O y , W z O y , V z O y , Mo z 0 y , YzO y , Ta z O y , .
  • a particularly preferred pure metal oxide is NiO.
  • a further particularly preferred pure metal oxide is ZnO.
  • a further particularly preferred pure metal oxide is Cr z O y .
  • the nanoparticles are selected from the group consisting of mixed metal oxides, preferably zinc containing mixed metal oxides, most preferably indium gallium zinc oxide (IGZO) , indium zinc oxide (IZO), zinc tin oxide (ZnSn0 3 ).
  • IGZO indium gallium zinc oxide
  • IZO indium zinc oxide
  • ZnSn0 3 zinc tin oxide
  • a further preferred mixed metal oxide is BaSn0 3 .
  • the nanoparticles are selected from the group consisting of doped metal oxides, particularly doped Ni z 0y, Zn z O y , Ti 2 0 y W z O y , V z 0 y , Mo z 0 y , Y z 0 y , Ta z O y , Cu z O y , Zr z O y , Sn z O y , In z O y and Nb z O y , most preferably NizOy, Zn x O y , Ti z O y , In z O y and Sn z O y .
  • Suitable dopants and amounts of dopants are known in the field.
  • the dopant atoms are incorporated into the ⁇ ⁇ crystal lattice either substitutionally or interstitially forming a homogeneous single-phase (a "solid solution") .
  • Specific examples include ITO (indium tin oxide; typical 90% ln 2 0 3 : 10% Sn0 2 ) , ATO (antimony doped tin oxide; typical 90% Sn0 2 : 10% Sb 2 0 3 ) and AZO (aluminum doped zinc oxide; typical 97% ZnO : 3% Al 2 0 3 ) .
  • separated multiphase systems e.g. M0 X + Fe 2 0 3
  • doped oxides can enable the fine tuning of the properties of the inventive thin films, such as electrical conductivity, work function and / or optical absorbance .
  • said metal oxides are doped with 0.001 - 30 wt%, preferably 0.01 - 15 wt%, most preferably 0.1 - 10 wt% (with respect to the metal), by one or more metals .
  • said dopant atoms are selected from the group consisting of transition metals, alkaline metals and earth-alkaline metals.
  • metal salts are physisorbed on the surface of the nanoparticles .
  • the term physisorbed is defined above. It is apparent that physisorption only takes place on the surface of the nanoparticles. Without being bound to theory, it is believed the metal salts act as a dispersant. In the context of the present inventions, metal salts are therefore termed dispersants.
  • the amount of metal salts physisorbed on the surface may vary over a broad range. Suitable amount of metal salts are in the range of 0.02-6 mol%, preferably 0.1-4 mol%, most preferably 0.2-2 mol% molar fraction of metal salt cation to metal atoms/ions in the nanoparticle . These amounts depend on the specific surface exhibited by the nanoparticles and may be determined by the skilled person.
  • the metal salt is of formula (I)
  • M represents a metal cation
  • R represents the corresponding salt anion
  • a is 2, 3, 4 or 5, preferably 2 or 3
  • b is 1, 2 or 3, preferably 1 or 2
  • the metal cation ( ) is preferably Zn, Al, Y, Pb, Bi, Cu, Ni, Co, Fe, Mn, Cr, V, Ti, La, Mg, Ca, Sr or Ba and is most preferably Zn, Al or Y.
  • the salt ion (R) is preferably acetate, formiate, citrate, oxalate, nitrate or halogenide and is most preferably acetate or nitrate.
  • the metal atom/ion of the dispersant salt differs from the metal atom/ion which is present in the major concentration in the nanoparticle.
  • the metal atom/ion of the dispersant salt differs from any metal atom/ion present in the nanoparticle which is present in a concentration larger than 0.1 wt% (relative to the nanoparticle composition)
  • metal salts described herein are commercial items. Such metal salts may be made by any method known in the art.
  • the invention provides a buffer layer with a composition as described herein wherein said layer consists of metal oxide nanoparticles and a dispersant as described herein.
  • said metal oxide nanoparticles are coated with one type of dispersant as defined herein.
  • said metal oxide nanoparticles are coated with two or more types of dispersant as defined herein.
  • either an individual nanoparticle is coated with said two or more types of dispersant or a first group on nanoparticles is coated with a first dispersant, a second group of nano- particles is coated with a second dispersant and so on.
  • the invention provides a buffer layer with the following composition: 70 - 99.9 wt%, preferably 80 - 99.5 wt%, most preferably 90 - 99 wt% metal oxide nanoparticles and 0.1-30 wt% metal salt, preferably 0.5-20 wt% metal salt, most preferably 1-10 wt% metal salt.
  • SIMS secondary ion mass spectrometry
  • the invention provides a buffer layer as described herein containing 70 - 99.9 wt%, preferably 80 - 99.5 wt%, most preferably 90 - 99 wt% NiO nanoparticles and 0.1-30 wt%, preferably 0.5-20 wt%, most preferably 1-10 wt% dispersant.
  • the invention provides a buffer layer as described herein containing 70 - 99.9 wt%, preferably 80 - 99.5 wt%, most preferably 90 - 99 t% ZnO nanoparticles and 0.1-30 t%, preferably 0.5-20 wt%, most preferably 1-10 wt% dispersant.
  • the invention provides a buffer layer as described herein containing 70 - 99.9 wt%, preferably 80 - 99.5 wt%, most preferably 90 - 99 wt% AZO nanoparticles and 0.1-30 wt%, preferably 0.5-20 wt%, most preferably 1-10 wt% dispersant.
  • the invention provides buffer layers as described herein comprising:
  • the invention provides an electronic device as described herein wherein said buffer layers have a film thickness of 3 - 1000 nm, preferably 10 - 500 nm. In one embodiment, monolayers, typically 3-30 nm thick are also envisaged. Thickness may be determined by profilometry, atomic force microscopy or electron microscopy .
  • the invention provides an optoelectronic device as described herein wherein said oxide nanoparticles have a primary particle diameter of 1 100 nm, preferably 3 - 50nm (measured by nitrogen absorption, X-Ray diffraction or transmission electron microscopy) .
  • the invention provides an electronic device as described herein wherein said oxide nanoparticles exhibit a bimodal or multimodal size distribution. It is believed that bimodal or multimodal size distributions result in higher particle packing densities, thus resulting in lower layer porosity.
  • the invention provides an electronic device as described herein wherein said buffer layers have a mean surface roughness below 100 nm, especially below 30 nm (determined by electron microscopy, atomic force microscopy or profilometry) .
  • the invention provides an electronic device as described herein wherein said buffer layer comprises, in addition to the nanoparticles as described herein, scattering particles.
  • buffer layers of the present invention may additionally comprise scattering particles, typically having a refractive index of > 2.3 and being comparatively large, typically with a particle size of 100 - 500 nm.
  • scattering particles typically having a refractive index of > 2.3 and being comparatively large, typically with a particle size of 100 - 500 nm.
  • the presence of such scattering particles provides for controlled Haze to an electronically functional buffer layer.
  • the use of such buffer layers with light scattering properties (Haze) is for light extraction (light outcoupling) in OLED devices or for light incoupling in solar cells, which enhances the efficiency of either device (more light gets into solar cell or more light is extracted from an OLED) .
  • Typical compositions of scattering particles are BaTi03, SrTi03, Ti02.
  • Typical concentrations of scattering particles in the dry buffer layer range from 5 - 50 wt%.
  • the invention provides an electronic device as described herein wherein said buffer layer has an electrical conductivity of 10 ⁇ 8 -10 3 S/cm, preferably 10 ⁇ 6 -10 2 , most preferably 10 ⁇ 3 -10 (determined by 4-point conductivity measurement).
  • the invention provides an electronic device as described herein wherein said buffer layer comprises scattering particles and has an electrical conductivity of ⁇ - ⁇ 3 S/cm.
  • the invention relates to an OLED wherein the ETL or EIL (i) is obtained by a method as described herein or (ii) consists of metal oxide nanoparticles coated with a dispersant as described herein.
  • the invention relates to an OLED wherein the HTL or HIL (i) is obtained by a method as described herein or (ii) consists of metal oxide nanoparticles coated with a dispersant as described herein.
  • the invention relates to an OLED wherein the device stack comprises the sequence electrode / HIL / HTL / active layer / ETL / EIL / electrode.
  • the invention relates to an OLED wherein the ETL layer consists of a monolayer of nanoparticles coated with a dispersant as described herein.
  • the invention relates to an organic solar cell (OPV) wherein the ETL (i) is obtained by a method as described herein or (ii) consists of metal oxide nanoparticles coated with a dispersant as described herein .
  • the invention relates to a perovskite solar cell wherein the HTL (i) is obtained by a method as described herein or (ii) consists of metal oxide nanoparticles coated with a dispersant as described herein.
  • the invention relates to an organic photodetector wherein the ETL (i) is obtained by a method as described herein or (ii) consists of metal oxide nanoparticles coated with a dispersant as described herein.
  • the invention relates to an electronic device wherein the ETL (i) is obtained by a method as described herein or (ii) consists of metal oxide nanoparticles coated with at least one type of a dispersant as described herein.
  • the invention relates to the use of metal oxide nanoparticles coated with metal salts as described herein for manufacturing an electronic device as described herein, particularly selected from the group of OLEDs, OPVs, perovskite type solar cells, photodetectorsand QLEDs.
  • the invention relates to an intermediate good (“a component") comprising a sheet-like substrate coated with a multitude of layers wherein at least one of said layers, preferably a buffer layer, comprises nanoparticles with physisorbed metal salts as defined in the first aspect of the invention.
  • the invention provides a component as defined herein, wherein said layers have the sequence substrate / electrode / HTL / active layer / ETL / electrode, ("normal architecture").
  • the invention provides a component as defined herein, wherein said layers have the sequence substrate / electrode / ETL / active layer / HTL / electrode, ("inverted architecture").
  • the invention provides a component as defined herein, wherein said layers comprise the sequence electrode / ETL / active layer / HTL.
  • This intermediate may also be the basis of a tandem cell.
  • the invention provides a component as defined herein, wherein said layers comprise the sequence electrode / HTL / active layer / ETL.
  • This intermediate may also be the basis of a tandem cell.
  • the invention provides a component as defined herein, wherein said layers comprise the sequence electrode / HTL / ETL / electrode.
  • the invention provides a component as defined herein, wherein said layers comprise the sequence electrode / ETL / HTL / electrode.
  • the invention provides a component as defined herein, wherein said layers have the sequences :
  • Non-transparent electrode/ ETL /active layer /HTL whereby the transparent electrode is selected from the group consisting of: PEDOT:PSS, Metal nanowires (including Silver nanowires, Copper nanowires, Nickel nanowires), metal grids, Graphene, Carbon nanotubes and ITO; and whereby the non-transparent electrode is selected from the group consisting of dense silver, dense aluminum, dense copper, dense gold, thick (opaque) carbon nanotube layer and thick (opaque) graphene-based layer.
  • PEDOT:PSS Metal nanowires (including Silver nanowires, Copper nanowires, Nickel nanowires), metal grids, Graphene, Carbon nanotubes and ITO
  • the non-transparent electrode is selected from the group consisting of dense silver, dense aluminum, dense copper, dense gold, thick (opaque) carbon nanotube layer and thick (opaque) graphene-based layer.
  • the invention provides a component as defined herein, wherein no additional layer is present.
  • the invention a component as defined herein, wherein the buffer layer has a thickness between 3-1000 nm, preferably 10-500 nm.
  • the invention provides a component as defined herein, wherein the buffer layer has a mean surface roughness below 30 nm.
  • the invention provides a component as defined herein, wherein the buffer layer has a metal salt content in the range of 0.1-30 wt%, preferably 0.5-20 wt%, most preferably 1-10 wt%.
  • the invention provides a component as defined herein, the substrate is as defined above .
  • the invention provides for the use of metal oxide nanoparticles comprising physisorbed metal salts as described herein for manufacturing of an intermediate good ("component") as defined herein.
  • the invention relates to a composition in the form of a suspension, said composition containing metal oxide nanoparticles, solvent (s) and a dispersant selected from the group of metal salts as described herein.
  • an intermediate good as defined herein or (ii) for manufacturing an electronic device as described herein; said device particularly selected from the group of OLEDs, OPVs, perovskite type solar cells, photodetectors and QLEDs.
  • suitable suspensions (II) comprise 0.2 - 50 wt-%, preferably 1 - 20 wt% nanoparticles (1) as described herein; 0.005 - 10 wt-%, preferably 0.01 - 5 wt- % metal salt (2) as described herein; 20 - 99.795 wt-%, preferably 30 - 98.99 wt-% solvent (4) as defined above, preferably water, dimethyl sulfoxide, dimethyl formamide, dimethyl acetamide, methanol, acetonitrile , ethylene glycol, propylene carbonate, acetone, 2 , 2 , 3 , 3-tetrafluoro- 1-propanol, most preferably methanol, acetonitrile, 2 , 2 , 3 , 3-tetrafluoro-l-propanol and water.
  • New Suspensions Further, certain of the above defined suspensions are novel and thus subject of the present invention. The term suspension is defined above.
  • the invention provides for a composition in the form of a suspension comprising (i) nanoparticles selected from the group of metal oxide nanoparticles and
  • Nanoparticles The amount of nanoparticles in the inventive composition may - depending on the intended use - vary over a broad range, but typically is in the range of 0.2 - 50 wt% (preferably 1 - 20 wt%) of the composition.
  • the nanoparticles in suspension have a hydrodynamic size D90 of less than 100 nm (measured by dynamic light scattering or centrifugal sedimentation techniques ) .
  • the nanoparticles are synthesized by a gas phase pyrolysis process, preferably flame spray synthesis.
  • Dispersants are discussed above and particularly include metal salts of formula (I) . Without being bound to theory, it is believed that the dispersants in the inventive suspension are partly physisorbed on the nanoparticles surface and partly dissolved in the solvent.
  • Solvents include polar solvents as discussed above, and are preferably selected from the group consisting of water, dimethyl sulfoxide, dimethyl formamide, dimethyl acetamide, methanol, acetonitrile , ethylene glycol, propylene carbonate, acetone, and 2 , 2 , 3 , 3-tetrafluoro-l-propanol .
  • polar solvents selected from the group consisting of methanol, acetonitrile, 2 , 2 , 3 , 3-tetrafluoro-l-propanol and water. It is understood that the term solvent also comprises combinations of the named above solvents.
  • the invention relates to the manufacturing of the inventive compositions, intermediate goods and devices disclosed herein and to inventive compositions, intermediate goods and devices obtained according to these methods. This aspect of the invention shall be explained in further detail below.
  • Manufacturing of suspensions The manufacturing of suspensions is a known procedure.
  • the coating of nanoparticles is also a known procedure. These procedures may be applied to the starting materials of the inventive suspensions .
  • solvent and nanoparticles are combined, for example by mixing, ultrasonication or ball milling.
  • the dispersants i.e. metal salts
  • Coating takes place at room temperature or upon heating and mixing.
  • solvent and dispersants i.e. metal salts
  • the nanoparticles are added. Coating takes place at room temperature or upon heating and mixing.
  • the intermediate goods according to the present invention may be obtained by solution processes. This is considered a significant advantage, as it enables manufacturing of all layers by simple technologies applicable to large areas and continuous processing.
  • the invention provides for a method for manufacturing an intermediate good as defined herein, wherein the buffer layer is manufactured comprising the steps of (a) applying a suspension on a substrate or coated substrate, said suspension comprising metal oxide nanoparticles coated with a dispersant and a solvent and removing the solvent from said composition and (b) removing the solvent from the obtained thin film and (c) optionally treating the dry layer at elevated temperature.
  • Step (a) Application of a suspension: Many processes are known to apply a liquid composition to a substrate to result in a wet thin film; a person skilled in the art is in a position to appropriately select. Suitable are, for example coating, particularly roll-to-roll-, slot-die-, spray-, ultrasonic spray-, dip-, reel-to-reel-, blade- coating; or by printing, particularly ink-jet-, pad-, offset-, gravure-, screen-, intaglio-, sheet-to-sheet- printing. Such processes are generally considered advantageous for large scale production, when compared to vacuum-based processes. Depending on the composition used in step (a), this step may be repeated (i.e. may be performed multiple times) . This embodiment is considered advantageous in order to fine tune the final film thickness .
  • Step (b) Drying and film formation Many processes are known to remove a liquid from a wet thin film of a coated substrate; a person skilled in the art is in a position to appropriately select. Suitable are, for example drying at room temperature or elevated temperature. Drying may take place in air, in a protecting gas, such as nitrogen or argon. Especially suited are gases with low humidity content (e.g. nitrogen, dry air, argon).
  • Step (c) Temperature cleaning step: A cleaning step in the form of a temperature annealing can optionally be conducted at temperatures below 150 °C.
  • the dried nanoparticle film in step (c) is annealed at 80°C - 150°C in air or in a protecting gas.
  • all layers of the intermediate good are manufactured by coating or printing.
  • Manufacturing of devices The manufacturing of devices starting from the above described intermediate goods is known per se, but not yet applied to the specific intermediate goods of the present invention.
  • the invention provides a method for manufacturing an electronic device as defined herein comprising the steps of (a) providing an intermediate good as defined herein, (b) contacting the layers of said good with an electrical circuit, (d) finishing the obtained product .
  • the electronic devices and intermediate goods are also novel. Due to the outstanding stability and performance obtained according to the inventive method, the suspensions are also novel.
  • the invention thus provides for a suspension obtained by a method comprising the step of combining metal oxide nanoparticles , dispersant ( s ) and solvent (s).
  • the invention thus provides for an intermediate good, obtained by a method comprising the steps of applying a suspension on a substrate or coated substrate, said suspension comprising (i) metal oxide nanoparticles coated with a dispersant and (ii) a solvent and removing the solvent from said composition and optionally treating the dry layer at elevated temperature.
  • the invention thus provides an electronic device, obtained by a method comprising the steps of providing an intermediate good as defined herein, contacting the layers with an electrical circuit, finishing the obtained product.
  • Example 1 Nickel oxide (NiO) nanoparticles were synthesized by flame spray synthesis.
  • 269.2g Ni-acetate tetrahydrate (Sigma Aldrich) was added to 1080g 2-ethylhexanoic acid (Aldrich) and dissolved by heating the mixture for 1 hour at 150°C.
  • 540g tetrahydrofuran (Sigma Aldrich) was added and well mixed.
  • the precursor then was fed (7 ml min -1 , HNP Mikrosysteme , micro annular gear pump mzr-2900) to a spray nozzle, dispersed by oxygen (15 1 min ⁇ 1 , PanGas tech.) and ignited by a premixed methane-oxygen flame (CH 4 : 1.2 1 min "1 , 0 2 : 2.2 1 min "1 ).
  • the off-gas was filtered through a glass fiber filter (Schleicher & Schuell) by a vacuum pump (Busch, Seco SV1040CV) at about 20 m 3 h" 1 .
  • the obtained oxide nanopowder was collected from the glass fiber filter.
  • the mean crystallite size was measured with a Rigaku MiniFlex 600, an SC-70 Detector, measured from 10° to 70° at 0.01° step size by using the Scherrer equation.
  • the mean crystallite size of the SrTi03 particles was 10 nm.
  • a dense and smooth layer of the above described NiO- suspension was deposited by spin coater at a speed of 4000 and followed by annealing at 140 °C for 15 minutes in air leading to a dry film thickness of ⁇ 30 nm.
  • the following steps were conducted in a nitrogen glovebox: Pbl 2 and CH3NH3I mixed with mole ratio of 1:1 with a concentration of ⁇ 40% were stirred in a mixture of dimethylformamide and dimethyl sulfoxide (2:1 v/v) at 60 °C for 12 h.
  • the as- prepared perovskite precursor solution was filtered using 0.45 pm PTFE syringe filter and coated onto the ITO/NiO substrate at a speed of 4, 000 r.p.m for 35 s.
  • the substrate (around 2.5 cm ⁇ 2.5 cm) was treated with chlorobenzene (CB) drop-casting.
  • CB chlorobenzene
  • the substrate was dried on a hot plate at 100 °C for 10 min.
  • a 2wt % PCBM solution in CB was spin- coated on the ITO/NiO/ APbI3 substrate at 1200 r.p.m for 30 s.
  • a 100-nm-thick Ag counter electrode was deposited through a shadow mask by thermal evaporation.
  • PCE photoconversion efficiency
  • Example 3 A variety of combinations of different types of nanopowders, metal salts and solvents were used for preparing suspensions. 5wt% of nanopowder, 0.25 wt% of metal salt and 94.75 wt% of solvent were dispersed by ball- milling for 15 minutes. The nanopowders were either prepared similarly to experiment 1 or were commercially available. The metal salts as well as solvents were all commercially available. The hereby prepared suspensions were evaluated after 3 days. The suspensions were considered instable if there was a phase separation such that there was a clear supernatant of 30% or more in height regarding to the total suspension filling height and were considered stable if less than 30% in height. The results are shown in the following table:
  • Nanopowder Metal Salt (I) Solvent Result (metal oxide) (disperant )
  • NiO Yttrium(III) nitrate Dimethyl sulfoxide stable hexahydrate
  • NiO Yttrium(III) nitrate 1 2-Propanediol stable hexahydrate
  • Example 4 5 wt% of the NiO-nanopowder from experiment 1, various amounts of Yttrium(III) nitrate hexahydrate (Aldrich) and methanol (Merck) were dispersed by ball- milling for 15 minutes. Stability was evaluated similar to Example 3. The following results were found: Suspension containing 0.005wt% and 0.025wt% of Yttrium(III) nitrate hexahydrate were found to be not stable (corresponding to 0.1 and 0.5 wt%, respectively), while a suspension containing 0.05wt% or more of Yttrium(III) nitrate hexahydrate (corresponding to 1 wt%) were found to be stable .
  • Example 5 Comparative example between this invention and Kim et al (Nanoscale Research Letters 2014, 9, 323) .
  • 5 wt% nanoparticles (ZnO; synthesized by flame spray pyrolysis) are dispersed in the solvent (ethanol or methanol) in the presence of 5 wt% dispersant (metal salt: Cs2C03 (according to Kim) or YN03x6H20 (this invention) , total dispersant concentration : 0.25 %).
  • the suspensions are prepared in analogy to example 4. Film coating was effected with a spin coater @5000rpm. Paricle size was determined with LUMISIZER by dissolution to 0.5 wt% ZnO in methanol. The results are provided below and in fig.5.
  • Optoelectronic devices comprising inventive nanoparticles are superior when compared to devices comprising known nanoparticles .

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Abstract

La présente invention concerne le domaine des dispositifs électroniques, tels que l'électronique organique, ledit dispositif comportant un substrat et une multitude de couches, au moins une desdites couches étant une couche tampon, ladite couche tampon comportant des nanoparticules d'oxyde métallique contenant des sels métalliques ayant subi une adsorption physique tel que décrit dans la spécification. L'invention concerne en outre des biens et des matériaux intermédiaires convenant à la fabrication de tels dispositifs électroniques, des procédés de fabrication et des utilisations spécifiques.
PCT/EP2016/000220 2015-02-12 2016-02-09 Dispositifs électroniques comportant des couches tampons d'oxyde métallique pouvant être traitées par solutions WO2016128133A1 (fr)

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KR1020177025149A KR102120534B1 (ko) 2015-02-12 2016-02-09 용액-가공성 금속 산화물 완충 층을 포함하는 광전자 장치
CA2974044A CA2974044A1 (fr) 2015-02-12 2016-02-09 Dispositifs electroniques comportant des couches tampons d'oxyde metallique pouvant etre traitees par solutions
SG11201706566XA SG11201706566XA (en) 2015-02-12 2016-02-09 Optoelectronic devices comprising solution-processable metal oxide buffer layers
CN201680010254.9A CN107251256B (zh) 2015-02-12 2016-02-09 包括溶液可处理的金属氧化物缓冲层的光电设备
JP2017542065A JP6503080B2 (ja) 2015-02-12 2016-02-09 溶液処理可能な金属酸化物バッファー層を含む光電子デバイス
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